Irreversible Work and Inner Friction in Quantum Thermodynamic Processes (original) (raw)
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What is the physical significance of entropy? What is the physical origin of irreversibility? Do entropy and irreversibility exist only for complex and macroscopic systems? Most physicists still accept and teach that the rationalization of these fundamental questions is given by Statistical Mechanics. Indeed, for everyday laboratory physics, the mathematical formalism of Statistical Mechanics (canonical and grand-canonical, Boltzmann, Bose-Einstein and Fermi-Dirac distributions) allows a successful description of the thermodynamic equilibrium properties of matter, including entropy values. However, as already recognized by Schrödinger in 1936, Statistical Mechanics is impaired by conceptual ambiguities and logical inconsistencies, both in its explanation of the meaning of entropy and in its implications on the concept of state of a system. An alternative theory has been developed by Gyftopoulos, Hatsopoulos and the present author to eliminate these stumbling conceptual blocks while maintaining the mathematical formalism so successful in applications. To resolve both the problem of the meaning of entropy and that of the origin of irreversibility we have built entropy and irreversibility into the laws of microscopic physics. The result is a theory, that we call Quantum Thermodynamics, that has all the necessary features to combine Mechanics and Thermodynamics uniting all the successful results of both theories, eliminating the logical inconsistencies of Statistical Mechanics and the paradoxes on irreversibility, and providing an entirely new perspective on the microscopic origin of irreversibility, nonlinearity (therefore including chaotic behavior) and maximal-entropy-generation nonequilibrium dynamics. In this paper we discuss the background and formalism of Quantum Thermodynamics including its nonlinear equation of motion and the main general results. Our objective is to show in a not-too-technical manner that this theory provides indeed a complete and coherent resolution of the century-old dilemma on the meaning of entropy and the origin of irreversibility, including Onsager reciprocity relations and maximal-entropy-generation nonequilibrium dynamics, which we believe provides the microscopic foundations of heat, mass and momentum transfer theories, including all their implications such as Bejan's Constructal Theory of natural phenomena.
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The unavoidable irreversible loss of power in a heat engine is found to be of quantum origin. Following thermodynamic tradition, a model quantum heat engine operating in an Otto cycle is analysed, where the working medium is composed of an ensemble of harmonic oscillators and changes in volume correspond to changes in the curvature of the potential well. Equations of motion for quantum observables are derived for the complete cycle of operation. These observables are sufficient to determine the state of the system and with it all thermodynamical variables. Once the external controls are set, the engine settles to a limit cycle. Conditions for optimal work, power and entropy production are derived. At high temperatures and quasistatic operating conditions, the efficiency at maximum power coincides with the endoreversible result η q = 1 − √ T c /T h . The optimal compression ratio varies from C = √ T h /T c in the quasistatic limit where the irreversibility is dominated by heat conductance to C = (T h /T c ) 1/4 in the sudden limit when the irreversibility is dominated by friction. When the engine deviates from adiabatic conditions, the performance is subject to friction. The origin of this friction can be traced to the noncommutability of the kinetic and potential energy of the working medium.
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Fluctuations of thermodynamic observables, such as heat and work, contain relevant information on the underlying physical process. These fluctuations are however not taken into account in the traditional laws of thermodynamics. While the second law is extended to fluctuating systems by the celebrated fluctuation theorems, the first law is generally believed to hold even in the presence of fluctuations. Here we show that in the presence of quantum fluctuations, also the first law of thermodynamics may break down. This happens because quantum mechanics imposes constraints on the knowledge of heat and work. To illustrate our results, we provide a detailed case-study of work and heat fluctuations in a quantum heat engine based on a circuit QED architecture. We find probabilistic violations of the first law and show that they are closely connected to quantum signatures related to negative quasi-probabilities. Our results imply that in the presence of quantum fluctuations, the first law o...
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